Luminescent graphene patterns

ABSTRACT

A luminescent nanocomposite comprising functionalized graphene and a luminescent moiety, its fabrication, and uses are described. The luminescent moiety is anchored non-covalently to the functionalized graphene. Luminescence properties of the nanocomposite may be modulated by choosing appropriate luminescent moieties such as native lactoferrin, native lactoferrin protected gold clusters, and so forth. Mechanical properties of the nanocomposite may be modulated by adding a biopolymer such as Chitosan. The nanocomposite may be used as a luminescent ink for encoding information, or a luminescent film for tagging articles of manufacture such as electronic waste components.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a divisional application of U.S. patentapplication Ser. No. 13/825,398, filed on Mar. 21, 2013, entitled“Luminescent Graphene Patterns,” which claims benefit of and priority toU.S. national stage filing under 35 U.S.C. §371 of InternationalApplication No. PCT/IB2012/001518, filed on Aug. 7, 2012, entitled“Luminescent Graphene Patterns,” which claims priority to Indian PatentApplication No. 2097/CHE/2012, filed on May 25, 2012 and entitled“Luminescent Graphene Patterns,” the disclosures of which are herebyincorporated by reference herein in their entireties.

BACKGROUND

Barcodes are the most common form of tagging used for tracking andidentifying objects—whether e-waste or otherwise. But barcodes canconvey very limited information since they encode a short bit string asa series of parallel bars in two colors. More recently, two dimensional(2D) matrices, commonly known as QR codes, have been developed and offera significantly higher information density. The method of readinginformation from a barcode or a QR code requires the surface on whichthese codes are printed to be of a certain minimum size and essentiallyflat. This poses a serious limitation on the use of such codes.

Waste, especially electronic waste (e-waste) comes in all shapes andsizes which may not always be amenable to tagging by barcodes or QRcodes. With increasingly stringent global regulations requiringmanufacturers and waste disposal companies to track their waste, abetter method for tagging and tracking objects is necessary.

Graphene, a 2D form of carbon, has been shown to have many specialproperties such as high mechanical stiffness, high elasticity, tunableband gap and excellent electron transport, potentially lending it tomany interesting applications. Conventionally, graphene is obtained byphysical exfoliation of graphite, but the method suffers from pooryield. Chemical methods such as chemical vapor deposition, chemicalreduction of graphite oxide, liquid phase exfoliation of graphite, andself-assembly are being researched for large-scale synthesis ofgraphene.

SUMMARY

In some embodiments, the present disclosure describes a luminescentnanocomposite composition made from graphene oxide, reduced grapheneoxide, or a combination thereof, and a luminescent moiety, wherein theluminescent moiety interacts non-covalently with the graphene oxide, thereduced graphene oxide or the combination thereof

In some embodiments, a method for preparing a luminescent film mayinclude heating a luminescent nanocomposite composition comprisinggraphene oxide, reduced graphene oxide or a combination thereof, and aluminescent moiety to a temperature from about 30° C. to about 50° C.,drying the composition to form a film, immersing the film in ammoniasolution, and washing the film to remove the ammonia.

In some embodiments, a method of labeling an article of manufacture witha removable and rewritable label may include depositing a luminescentnanocomposite composition on the article of manufacture, wherein theluminescent nanocomposite composition comprises graphene oxide orreduced graphene oxide, or a combination thereof, and at least oneluminescent moiety, wherein the luminescent moiety interactsnon-covalently with the graphene oxide or reduced graphene oxide.

In some embodiments, an article of manufacture may comprise a removableand rewritable label, wherein the label is comprised of a luminescentnanocomposite composition comprising graphene oxide, reduced grapheneoxide, or a combination thereof, and a luminescent moiety, wherein theluminescent moiety interacts non-covalently with the graphene oxide, thereduced graphene oxide or the combination thereof.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1: (A) Photograph of a representative large area composite film.Inset shows the photograph of the folded film showing the flexibility ofthe film. SEM images of the films showing (B) the folded film edge, (C)surface of the film, and (D) higher magnification image of across-section of the film showing the layer-by-layer nature of filmformation. Multiple layers are visible.

FIG. 2: SEM images of different patterns ascribed on representative RGOcomposite films. A number of patterns are shown in (A), (C), and (E) andtheir expanded views are shown in (B), (D), and (F), respectively.

FIG. 3: SEM images of the same part of the film after three rounds ofpatterning and erasure. (A) low-magnification image and (B) highermagnification image of the inside portion. No trace of pattern can beseen. In the left side images, only one edge of the free-standingcomposite film is shown. The area outside the film is the carbon tapeused for fixing the film.

FIG. 4: Characterization of representative large area luminescentpatterns. (A) Optical image of the pattern, (B) Raman spectral imagecollected from the pattern and (C) spectra from two locations of theimage marked in (B). Color of the spectral traces corresponds to thelocations, indicated in image (B). Raman spectral images generated (D)from the fluorescence of Au@NLf and (E) from the frequency range of1300-1600 cm⁻¹ corresponding to D- and G-bands of RGO.

DETAILED DESCRIPTION

A desirable quality for using a nanomaterial for waste tracking is thatit can be inexpensive and amenable to large-scale synthesis. Of the manypotential nanomaterials, graphene is particularly promising. In someaspects, luminescent nanocomposite compositions are described. Thenanocomposite composition, the methods of making the nanocompositecomposition, and the methods of using the nanocomposite composition asdescribed herein, are not limited to a single composition or a singleprocess.

In some embodiments, the composition may comprise graphene oxide,reduced graphene oxide, or any combination thereof. Functionalizedgraphene is capable of non-covalently interacting with a variety ofluminescent moieties. As such, graphene functionalized with anyfunctional group may be used for this composition. In some embodiments,the composition may comprise sulfonated graphene, fluorinated graphene,or chlorinated graphene, or any combination thereof

Proteins, non-protein molecules and polymers that exhibit luminescencemay form clusters with transition metal atoms, transition metal ions,rare-earth metal atoms, or rare-earth metal ions, or any combinationthereof. The color of luminescence of such clusters is determined by theoxidation state of the metal atom or ion as well as the luminescentproperties of the cluster forming molecules. Luminescent moieties withpositive and negative functionalities maybe attached electrostaticallyto graphene oxide or appropriately functionalized graphene. In someembodiments, the luminescent moiety may comprise a protein such as, forexample, native lactoferrin protein (NLf), bovine serum albumin, orlysozyme. In other embodiments, the luminescent moiety may comprise asmall molecule such as, for example, glutathione or cysteine.

In some embodiments, the luminescent moiety may comprise a transitionmetal including, but not limited to, Au (gold), Ag (silver), Cd(cadmium), Se (selenium), or Hg (mercury), or any combination thereof Inother embodiments, the luminescent moiety may comprise a rare-earthmetal including, but not limited to, Eu (Europium).

Any cluster having a positive functionality can be anchored intographene. The composition may be configured to allow anchoring of morefunctional groups than allowed by graphene alone by adding a polymer. Insome embodiments, the composition may comprise one or more polymers suchas, for example, chitosan, poly acrylic acid, polypyrrole, poly (allylmethacrylate), poly(vinylidene fluoride),poly(2-methoxy-5-(2′ethyl-hexyloxy)-1,4-phenylene vinylene), and thelike.

In general, any luminescent moiety can be anchored to appropriatelyfunctionalized graphene as long as the functionality of graphene hasopposite charge to that of the luminescent moiety under normalconditions. Any combination of luminescent moieties may also be anchoredto the appropriately functionalized graphene. One can envision variouscombinations of luminescent moieties and graphene functionalities forcreating a diverse set of nanocomposites that luminesce across theoptical spectrum tailored to specific applications. The specificcombination of the luminescent moiety and the functional group ofgraphene will determine the wavelength (color) of luminescence of thenanocomposite. In some embodiments, the composite may comprise grapheneoxide and NLf. In other embodiments, the composite may comprise grapheneoxide and NLf-protected gold clusters (Au@NLf). In yet otherembodiments, the composite may comprise reduced graphene oxide and NLf.In certain embodiments, the composite may comprise reduced grapheneoxide and Au@NLf, and in particular embodiments, the composite maycomprise reduced graphene oxide, NLf, and chitosan.

In some aspects, methods of preparing a luminescent nanocompositecomposition are described. Such a composition may be used as, forexample, a luminescent ink which may be invisible under normalcircumstances and may reveal itself only when exposed to certain lightconditions such as, for example, ultra-violet light. Invisible inks mayhave uses in secure data transfer for military, government, orconfidential private communications.

In some embodiments, functionalized graphene is suspended in water, aluminescent moiety is suspended in water at an appropriateconcentration, and known volumes of the two suspensions are mixed andstirred for a sufficient time to form the luminescent nanocompositesuspension. In some embodiments, the water may be purified water,deionized water, or distilled water.

Whereas, the concentration of functionalized graphene suspension willdepend on the extent of functionalization of graphene being used, insome embodiments, the concentration of functionalized graphene is fromabout 0.01 wt % to about 1 wt %. “wt %” refers to the percent ratio ofthe weight of graphene present in a solvent to the weight of the solventand the graphene combined to prepare the suspension. For example, if 0.5g of graphene is suspended in 99.5 g (i.e., 99.5 ml) of water, theconcentration of graphene is 0.5 wt %. In some embodiments, comprisingsulfonated graphene, up to about 0.2 wt % graphene may be used. In otherembodiments comprising reduced graphene oxide, up to about 0.05 wt %graphene may be used. Polymers like chitosan can assisting in dispersinggraphene in water. As such, in some embodiments wherein, polymers likechitosan are present in the suspension, a higher concentration ofgraphene of up to about 1 wt %, up to about 0.9%, or up to about 0.8%may be used.

In some embodiments, a chitosan solution is added to the aqueous mixturecomprising the luminescent nanocomposite. The chitosan solution maycomprise about 0.2% to about 2% chitosan by weight in a dilute acidsolution. In some embodiments, the chitosan solution may comprise about0.2% to about 1.8% by weight, about 0.2% to about 1.6% by weight, about0.2% to about 1.4% by weight, about 0.2% to about 1.2% by weight, about0.2% to about 1.0% by weight, about 0.4% to about 2% by weight, about0.6% to about 2% by weight, about 0.8% to about 2% by weight, about 1.0%to about 2% by weight, about 0.4% to about 1.8% by weight, about 0.6% toabout 1.6% by weight, about 0.8% to about 1.4% by weight, or about 1.0%to about 1.2% by weight. In some embodiments, the acid may be an acidsuch as, for example, acetic acid, nitric acid, or hydrochloric acid. Insome embodiments, the ratio of volume of the aqueous mixture comprisingthe luminescent nanocomposite to volume of chitosan solution may be fromabout 1:0.1 to about 1:0.5.

In certain applications, such as, for example, labeling an article ofmanufacture, it may be desired to form luminescent films. Oneapplication of luminescent nanocomposite films is for tagging andtracking waste articles which may be too small in size to be tagged by atraditional barcode or a QR code, or may not have a flat surfacenecessary for affixing a traditional barcode or a QR code. In someaspects, the present disclosure describes methods of preparingluminescent films. In some embodiments, a luminescent film maybe formedusing a self-drying methodology. In some embodiments, the luminescentnanocomposite composition described above is heated for a time to drythe composition to form a film, followed by immersing the film in adilute basic solution, followed by washing the film with, for example,one or more of water, ethanol, or methanol repeatedly to remove thebasic solution. In some embodiments, the water may be distilled water ordeionized water. In certain embodiments, the composition may be heatedto temperatures of about 20° C., about 25° C., about 30° C. , about 35°C., about 40° C., about 45° C., about 50° C., about 55° C., about 60°C., about 65° C., about 70° C., or any range between any two of thesetemperatures. In some embodiments, the composition may be dried by, forexample, freeze drying, vacuum drying, and/or the like. In certainembodiments, the dilute basic solution may include, but is not limitedto, ammonia solution, dilute sodium hydroxide solution, or dilutepotassium hydroxide solution. In particular embodiments, the luminescentmoiety may include, but is not limited to, NLf or Au@NLf. In otherembodiments, the luminescent composition may comprise other polymerssuch as, for example, chitosan.

In some aspects, methods of using the luminescent nanocompositecompositions are described. In some embodiments, the luminescentnanocomposite composition may be used as a luminescent invisible ink forprinting data, that is visible only under specific conditions, such as,for example, under ultraviolet light. In some embodiments, theluminescent nanocomposite may be used in the form of films for labelingan article of manufacture. Examples of luminescent nanocompositecompositions for such use include, but are not limited to, a luminescentnanocomposite composition comprising graphene oxide and NLf, aluminescent nanocomposite composition comprising graphene oxide andAu@NLf, a luminescent nanocomposite composition comprising reducedgraphene oxide and NLf, and a luminescent nanocomposite compositioncomprising reduced graphene oxide and Au@NLf. In some embodiments, theluminescent nanocomposite composition may be deposited on an article ofmanufacture as a transparent thin film. In other embodiments, theluminescent nanocomposite composition may be deposited on an article ofmanufacture by spraying a surface of the article of manufacture or bystamping a surface of the article of manufacture. In some embodiments,the luminescent nanocomposite composition maybe deposited in the form ofa barcode or a QR code. The article of manufacture in above mentionedcases may be waste articles such as, for example, discarded electroniccomponents, spent printing cartridges, biological waste, chemical waste,radioactive waste, and so forth.

The data can generally be any type of data, such as text, numbers,symbols, images, musical notes, barcodes, computer code, and so on. Insome cases, the data can be data that one wishes to remain confidentialor to at least limit the number of individuals who can read or accessthe data.

In some embodiments, the label comprising the luminescent nanocompositecomposition film may be detected under special conditions such as, forexample, under ultraviolet light. Examples of detectors that may be usedfor detecting labels made from the luminescent nanocomposite filmsinclude, but are not limited to, ultraviolet luminescence sensors,fluorescence spectrometers, Raman spectrometers, and the like.

In some aspects, an erasable, rewritable luminescent label for anarticle of manufacture is described. The label may be created using theluminescent nanocomposite composition described herein above, either inthe form an ink or as a film. In some embodiments, the label may beerased by removing the luminescent moiety from the nanocompositecomposition or film by wetting the label. In other embodiments, adifferent luminescent moiety may be added to the nanocompositecomposition or film, to form a second label. In other embodiments, aplurality of different luminescent moieties may be added tonanocomposite composition(s) or film(s), to form a plurality of labels.In some embodiments, the luminescent nanocomposite label may be affixedto an article that may not have a flat surface or may be too small foraffixing a traditional barcode or QR code label. Examples of articles ofmanufacture that can be labeled using the luminescent nanocompositedescribed herein include, but are not limited to, electronic componentsuch as, for example, printed circuit boards, discarded batteries,discarded LCD displays, spent printing cartridges, and the like; orhazardous waste such as, for example, explosives, radioactive waste,biological waste, and the like. In other embodiments, the luminescentnanocomposite may be used as luminescent inks for imprinting andtransferring secure or confidential data for, without limitation,military, government of private industry use. The luminescentnanocomposite inks may be tailored to vanish after a pre-designed periodof time, or may be made removable by wetting. The susceptibility of thelabel to water can be modified by coating one or more layers on top ofthe label to limit or control access of water to the label. The layersmay be configured to be removable when desired. Examples of layers thatmay be used include, but are not limited to, a shrink wrap film, astretch wrap film, a cling wrap film, an adhesive plastic film, a lowdensity polyethylene film, PVC films, a wax paper, and the like.

In some aspects, the present disclosure describes an article ofmanufacture that includes a removable and rewritable label comprisingthe luminescent nanocomposite described above. In particularembodiments, the label may comprise graphene oxide and NLf. In otherembodiments, the label may comprise reduced graphene oxide and NLf. Insome embodiments, the label may comprise graphene oxide and Au@NLf. Inother embodiments, the label may comprise reduced graphene oxide andAu@NLf. In yet other embodiments, the label may comprise chitosan inaddition to the functionalized graphene oxide and the luminescentmoiety.

EXAMPLES

Embodiments illustrating the method and materials used may be furtherunderstood by reference to the following non-limiting examples.

Example 1: Pre-Oxidation of Graphite

In a 250 mL beaker, concentrated H₂SO₄ (25 mL), 5 g of K₂S₂O₈ and 5 g ofP₂O₅ were taken and heated to 90° C. with constant stirring. After allthe reactants were completely dissolved, the reaction temperature wasdecreased to 80° C. To this reaction mixture, 6 g of graphite powder wasadded slowly. Bubbling was observed initially and subsided subsequently,over a period of 30 minutes. Temperature of the reaction mixture wasmaintained at 80° C. for 5 hours. Heating was stopped and the mixturewas diluted with 1 L of distilled water and left undisturbed overnight.The resultant solution was then filtered and washed to remove excessacid. The solid product was dried in air overnight to yield pre-oxidizedgraphite.

Example 2: Oxidation to Graphite Oxide (GO)

230 mL of concentrated H₂SO₄ was maintained at 0° C. using an ice bath.Pre-oxidized graphite was then added to this and stirred. 15 g of KMnO₄was added slowly making sure that the temperature never went beyond 10°C. Then, the temperature was raised to 35° C. and allowed to react for 2hours. Subsequently, 1 L of distilled water was added carefully keepingthe temperature below 50° C. The reaction mixture was stirred for 2hours and then 1.5 L of distilled water and 25 mL of 30% H₂O₂ wereadded. The mixture was kept at room temperature for a day and thesupernatant was decanted. The remaining solution was centrifuged andwashed with 10% HCl followed by distilled water. This was repeatedseveral times. The resultant solid was dried and 2% (w/w) dispersion wasprepared in distilled water. This dispersion was dialyzed for 3 weeks toremove all unwanted contaminants like salts and acid. Then thedispersion was diluted to 0.1% (w/w).

Example 3: Hydrothermal Deoxygenation of Graphene Oxide (GO) to ReducedGraphene Oxide Nanosheets

Reduction of GO was performed by the hydrothermal method. In a typicalsynthesis procedure, GO was sonicated for 45 minutes. (CREST TRU-SWEEP27D, 50 Hz) to exfoliate the suspension completely and centrifuged at5000 rpm to remove the unexfoliated GO. About 50 mL of the purifiedexfoliated GO solution (0.05 wt %) was transferred to a Teflon-linedhydrothermal reaction vessel and heated at 180° C. for 6 hours. After 6hours, the vessel was cooled to room temperature. A black precipitate ofRGO settles at the bottom. This was redispersed in distilled water bymild sonication.

Example 4: Sulfonation of RGO

To increase the stability of graphene in water, sulfonic acid groupswere introduced onto RGO surface through a simple sulfonation procedure.20 mg sulfanilic acid and 8 mg sodium nitrite were firstly dissolved inNaOH solution (0.25%). Then 4 mL, 0.1 M HCl was added to the abovemixture and kept in an ice bath under stirring. After 15 minutes, aryldiazonium salt solution was added to 20 mL, 0.5 mg/mL RGO dispersionwith continuous stirring for 2 hours in an ice bath. After 2 hours, thesolution was filtered and washed and redispersed in distilled water witha final concentration of 0.05 wt %. The pH of the solution was measuredto be around 6.

Example 5: Preparation of Au@NLf

Au@NLf quantum clusters were synthesized by the following procedure: NLfand HAuCl₄ were mixed and stirred continuously for 5 minutes. Requiredamount of 1 M NaOH was added to the above mixture such that the finalconcentration was 5%. The mixture was stirred for 24 hours which resultsin the formation of Au@NLf. Au@NLf refers to a mixture of clusters,dominated by a cluster containing 25 atoms of gold, along with minorfractions of Au₁₃, which are protected by the protein molecule.

Example 6: Preparation of RGO/GO-NLf and RGO/GO-Au@NLf Composites

NLf was anchored onto RGO/GO substrate through a simple electrostaticinteraction. To 5 mL GO/RGO (0.02 wt %), different volumes of NLf (12mg/mL) was added. The sample was stirred for 2 hours and stored at 4° C.for further use. Similar method was used to make GO/RGO-Au@NLfcomposites in which known volume of Au@NLf was added to 5 mL of GO/RGOand stirred for 2 hours. The mixture was stored for further use at 4° C.Example 7: Preparation of RGO-NLf-Ch Composite

Chitosan (Ch) is known to form composites with RGO. GO/RGO-NLfcomposites prepared as mentioned above were mixed with Ch solution (0.8%chitosan in 1.5% acetic acid) in 1:0.3 ratio (v/v). The mixture wasstirred continuously for 2 hours. The homogeneous dispersion was thenkept at 4° C. for further use. Similarly, GO/RGO-Au@NLf-Ch was alsoprepared by replacing NLf with Au@NLf in the above procedure.

Example 8: Preparation of RGO-Ch-NLf/Au@NLf Film

The above solution(s) were transferred to a Petri dish and kept in anoven maintained at 40° C. The mixture was allowed to dry and aftercomplete drying, the film was immersed in ammonia solution (5 vol. %)for 15 minutes. Then, the films were washed repeatedly with distilledwater to remove ammonia. This film can be easily peeled off for furtheruse. For preparing red luminescent films, NLf was replaced with Au@NLfclusters.

The properties of the fabricated composites were studies usingUV/Visible spectroscopy, Fourier Transform Infrared spectroscopy,Transmission and Scanning Electron microscopy, Photoluminescence andRaman spectroscopy.

Example 9: Addition of Luminescence

A luminescent iron binding protein, lactoferrin (NLf) or NLf protectedAu clusters (Au@NLf) electrostatically was anchored at nearly neutralpH. The pH of GO and RGO dispersion was around 6.5. At this pH, thenegatively charged functional groups will be in the ionized state makingGO and RGO highly dispersible in water. The presence of negativelycharged functional groups on RGO/GO was used for the formation ofcomposites. The samples were characterized by Raman spectroscopy whichshowed a strong D-band pointing to the highly functionalized grapheme.The composite exhibited a weak bluish-green luminescence. Bright redluminescence was imparted to the composite by anchoring the proteinprotected clusters (Au@NLf) instead of pure NLf.

Example 10: Large Area Films: Properties and Applications

Large area RGO/GO based composite films were fabricated through a simpleself-drying methodology as described above. Upon solvent evaporation,the composites formed large area films aided by chitosan. The presenceof RGO increased the mechanical strength of the film. FIG. 1A belowshows the photograph of macroscopic films. The as-fabricated films werefound to be highly flexible (inset FIG. 1A). The film was characterizedusing SEM, Raman and fluorescence spectroscopy. FIGS. 1 B-D show the SEMimages of the film. The SEM image of a folded edge of a film is shown inFIG. 1B, emphasizing the flexible nature. The film surface was found tobe smooth (FIG. 1C). Higher magnification image of the edge of the filmshowed that it is formed by layer-by-layer assembly (FIG. 1D). Theluminescence of the composite was found to be stable at a good window ofpH and temperature windows, increasing the applicability of thecomposite.

Example 11: Erasable Patterns and Applications

Large area patterns were inscribed on the prepared films. Luminescentpatterns can also be fabricated through this methodology byincorporating NLf/Au@NLf in the composite. The inscribed pattern can beerased from the films and another pattern can be inscribed. Erasable andrewritable patterns may be useful in security coding and confidentialdata transfer. FIGS. 2A and B show the film after imprinting the firstpattern. The pattern was erased by simply wetting of the film usingwater. After drying the film, a second pattern was inscribed. FIGS. 2Cand D show the SEM images of this pattern. This pattern was also erasedby wetting the film and a third pattern was inscribed (FIGS. 2E and F).The film after erasure also was analyzed using SEM. No trace ofimprinted pattern was seen, pointing to the complete erasure of thepattern (FIG. 3). The erasure and patterning can be done repeatedly. TheRaman measurement clearly shows that the formed patterns are luminescent(FIG. 4). No significant change in florescence intensity was seen whenexposed to a wide range of metal ions, change in pH (5-9), andtemperature (10-50° C.).

Example 12: Protecting the Label from Water

A metal box was labeled with a luminescent composite pattern in the formof a bar-code. This bar-code was readable under ultraviolet light(standard forensic black light). The box was then inserted in a tankfilled with water and agitated for about 2 minutes. Upon removal fromthe tank, the bar-code could no longer be read under ultraviolet lightshowing that the luminescent pattern was lost in water.

A separate metal box was labeled with another luminescent compositepattern in the form of a bar-code. A thin plastic film was thenlaminated on top of the luminescent pattern. It was confirmed thatbar-code was readable under ultraviolet light. The box was then insertedin a tank filled with water and agitated for about 2 minutes. Uponremoval from the tank, the bar-code was still readable under ultravioletlight confirming that a laminated plastic film protected the luminescentpattern from exposure to water. One may be able to substitute thelaminated plastic film with other materials depending on the usage andbase materials.

In the above detailed description, reference is made to the accompanyingdrawings, which form a part hereof. In the drawings, similar symbolstypically identify similar components, unless context dictatesotherwise. The illustrative embodiments described in the detaileddescription, drawings, and claims are not meant to be limiting. Otherembodiments may be used, and other changes may be made, withoutdeparting from the spirit or scope of the subject matter presentedherein. It will be readily understood that the aspects of the presentdisclosure, as generally described herein, and illustrated in theFigures, can be arranged, substituted, combined, separated, and designedin a wide variety of different configurations, all of which areexplicitly contemplated herein.

This disclosure is not limited to the particular systems, devices andmethods described, as these may vary. The terminology used in thedescription is for the purpose of describing the particular versions orembodiments only, and is not intended to limit the scope.

As used in this document, the singular forms “a,” “an,” and “the”include plural references unless the context clearly dictates otherwise.Unless defined otherwise, all technical and scientific terms used hereinhave the same meanings as commonly understood by one of ordinary skillin the art. Nothing in this disclosure is to be construed as anadmission that the embodiments described in this disclosure are notentitled to antedate such disclosure by virtue of prior invention. Asused in this document, the term “comprising” means “including, but notlimited to.”

The present disclosure is not to be limited in terms of the particularembodiments described in this application, which are intended asillustrations of various aspects. Many modifications and variations canbe made without departing from its spirit and scope, as will be apparentto those skilled in the art. Functionally equivalent methods andapparatuses within the scope of the disclosure, in addition to thoseenumerated herein, will be apparent to those skilled in the art from theforegoing descriptions. Such modifications and variations are intendedto fall within the scope of the appended claims. The present disclosureis to be limited only by the terms of the appended claims, along withthe full scope of equivalents to which such claims are entitled. It isto be understood that this disclosure is not limited to particularmethods, reagents, compounds, compositions or biological systems, whichcan, of course, vary. It is also to be understood that the terminologyused herein is for the purpose of describing particular embodimentsonly, and is not intended to be limiting.

With respect to the use of substantially any plural and/or singularterms herein, those having skill in the art can translate from theplural to the singular and/or from the singular to the plural as isappropriate to the context and/or application. The varioussingular/plural permutations may be expressly set forth herein for sakeof clarity.

It will be understood by those within the art that, in general, termsused herein, and especially in the appended claims (e.g., bodies of theappended claims) are generally intended as “open” terms (e.g., the term“including” should be interpreted as “including but not limited to,” theterm “having” should be interpreted as “having at least,” the term“includes” should be interpreted as “includes but is not limited to,”etc.). It will be further understood by those within the art that if aspecific number of an introduced claim recitation is intended, such anintent will be explicitly recited in the claim, and in the absence ofsuch recitation no such intent is present. For example, as an aid tounderstanding, the following appended claims may contain usage of theintroductory phrases “at least one” and “one or more” to introduce claimrecitations. However, the use of such phrases should not be construed toimply that the introduction of a claim recitation by the indefinitearticles “a” or “an” limits any particular claim containing suchintroduced claim recitation to embodiments containing only one suchrecitation, even when the same claim includes the introductory phrases“one or more” or “at least one” and indefinite articles such as “a” or“an” (e.g., “a” and/or “an” should be interpreted to mean “at least one”or “one or more”); the same holds true for the use of definite articlesused to introduce claim recitations. In addition, even if a specificnumber of an introduced claim recitation is explicitly recited, thoseskilled in the art will recognize that such recitation should beinterpreted to mean at least the recited number (e.g., the barerecitation of “two recitations,” without other modifiers, means at leasttwo recitations, or two or more recitations). Furthermore, in thoseinstances where a convention analogous to “at least one of A, B, and C,etc.” is used, in general such a construction is intended in the senseone having skill in the art would understand the convention (e.g., “asystem having at least one of A, B, and C” would include but not belimited to systems that have A alone, B alone, C alone, A and Btogether, A and C together, B and C together, and/or A, B, and Ctogether, etc.). In those instances where a convention analogous to “atleast one of A, B, or C, etc.” is used, in general such a constructionis intended in the sense one having skill in the art would understandthe convention (e.g.,“ a system having at least one of A, B, or C” wouldinclude but not be limited to systems that have A alone, B alone, Calone, A and B together, A and C together, B and C together, and/or A,B, and C together, etc.). It will be further understood by those withinthe art that virtually any disjunctive word and/or phrase presenting twoor more alternative terms, whether in the description, claims, ordrawings, should be understood to contemplate the possibilities ofincluding one of the terms, either of the terms, or both terms. Forexample, the phrase “A or B” will be understood to include thepossibilities of “A” or “B” or “A and B.”

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, such as in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” and the like include the number recited andrefer to ranges which can be subsequently broken down into subranges asdiscussed above. Finally, as will be understood by one skilled in theart, a range includes each individual member. Thus, for example, a grouphaving 1-3 cells refers to groups having 1, 2, or 3 cells. Similarly, agroup having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 cells,and so forth.

Various of the above-disclosed and other features and functions, oralternatives thereof, may be combined into many other different systemsor applications. Various presently unforeseen or unanticipatedalternatives, modifications, variations or improvements therein may besubsequently made by those skilled in the art, each of which is alsointended to be encompassed by the disclosed embodiments.

What is claimed is:
 1. A luminescent nanocomposite compositioncomprising: graphene oxide, reduced graphene oxide, or a combinationthereof; and at least one luminescent moiety, wherein the luminescentmoiety non-covalently interacts with the graphene oxide, or reducedgraphene oxide, or combination thereof.
 2. The nanocomposite compositionof claim 1, wherein the luminescent moiety is native lactoferrin, ornative lactoferrin-protected gold cluster, or a combination thereof. 3.The nanocomposite composition of claim 1, further comprising chitosan.4. The nanocomposite composition of claim 1, comprising graphene oxideand native lactoferrin.
 5. The nanocomposite composition of claim 1,comprising graphene oxide and native lactoferrin-protected gold cluster.6. The nanocomposite composition of claim 1, comprising reduced grapheneoxide and native lactoferrin.
 7. The nanocomposite composition of claim1, comprising reduced graphene oxide and native lactoferrin-protectedgold cluster.
 8. The nanocomposite composition of claim 1, comprisingreduced graphene oxide, native lactoferrin, and chitosan.